Vinylidene chloride compositions



Petented Sept. 18, 1945 VINYLIDENE CHLORIDE COMPOSITIONS Edger C. Britten and Harold W. Moll, Mldlimd, Mich, assignors to The DowChemicnl Company, Midland, Miolm, a corporation or Michi- No Drawing. Application July 18, 1941, Serial N- 03,011

2 Claims. :(Cl. 260-42) This invention relates to thermoplastic compo-' sitions comprising polymeric vinylidene chloride named, which may be obtained by polymerizing together monomeric vinylidene chloride and one or more of the monomers of other polymerizable moteriels, such as vinyl chloride, vinyl acetate.

vinyl ethers, acrylic and methacrylic acids and esters thereof, acrylic nitrile, butsdiene, styrene, ellyl chloride and the allyl, methallyl, crotonyl, 2-chioroellyl, or cinnemyl esters of mono and dicerboxylic acids. The polymer of vinylidene chloride alone is described in U. S. Patent No. 2,160,903 and many of its co-polymers with other polynierizeble compounds, as well as certain plasticized compositions comprising these co-polymere, and weys in which the products may be mode, are described in U. S. Patents 2,160,904; 2,206,022; 2,215,379 and 2,160,931 to 2,160,948, inclusive.

.The ellcyd resins which may he used in the present invention include all those complexes resulting: primerily from the intercction of a. polyhydric alcohol with e nolyloesic acid or its anhydride, such as for example, the product resulting from the reaction of glycerine end nhtlielic enhydride, with or without other renoting: scents. They are grouped broadly into three types, namely, oxidizing, non-oxidizing and modified. They may he further classed as, (1) heat non-convertible, that is, they do not gelon heetine, (2) heat convertible, that is, heat treetment converts them into infusible and insoluble products, (3) element convertible, that is, those derived from unsaturated acids or alcohols, the p operties of which sire irreversibly altered by oxidation of the unsetureted component by the elements. The alwd resins may be modified by reection with drying and non-drying oils and their acids, or with neturcl or other synthetic resins.

Enemples of slls'yd resins mentioned in the preceding peregrnph ere characterized by the following definitions from the trade catalogues of the various compenies supplying such resins:

Esterol 830 (Peremet): Pure eliryd resin free of phenol; 50% solids, 50% toluol; sp. 3., 0.9%;

air dry: set to touch 415-60", tech free, 3-4 hrs; belie 1% hrs. at l00-220 F; immiscible with oils and short oil varnishes; 8.20 lbs. per cell. at 25 C.; acid value, -12; color (l-lellige-Klett), 1L; viscosity (Gerdner-Holdt), Q-R; solubility complete in all cool tor solvents and commonly used lacquer solvents.

Dnreplen (3- .5 (Resinous Products): 58-62% 8.0; acid number, 100; resin 5-15; color-% solids (Inst. P. & V. R.), 6-8; air dry -90 min; bake 2-3 hrs. 180-225 F.; viscosity 0-!" at 4.0% M. T.

Tolerance: M. T.%; Q body oxidizingoil: resin-5M0; chlorinated rubber-100%; varnish/resin-ZO/iii).

Rezyi 1103 (American Cyanaxnide): Liquid resin. Not supplied in solution. Lbs/gel. 9.0; re free. index 20 C.-l.512; acid number28-33 color (I. P. 8: V. R.)-1L-.-2L; bake 2-3 hrs. at 180-220 FE; completely compatible with mineral spirits, Noe-cellulose, Cl-rubher. 75% drying oils, 30% to ethyl cellulose.

Aroplaz 930 (S 8; W Corp): Percent N. V.- 100; viscosity-(G. H. V-W; viscosity (noises) 08-1031; acid value 4-6; color (G. H.-l033)- 810, color (Hellige)-3L-4'; lbs/gel. 20 C. (pinstic 0.57; solution 8.57); short, pure, non-oxidizing alkyd.

Amberlec D-96 (Resinous Products): Hard,-

slightly plastic. Initial softening pomt-'70-02 (3.; color (Rosin scale)approx. hi1; ncid number 30-50. Somewhat flexible.

Persnol LB-e (modified meleic type resin) (Peramet): Acid number-424i; M. P.--220- 230 F.; color (extra. light)-WG; sp. g.l.l.l; lbs./ga.l.-9.30. Solubility complete in mineral spirits, all coal tar solvents and commonly used lacquer solvents. Ins. in alcohol.

Lewisol 2L (Lewis): Color-N-WG; M. P.- l30l40 0.; acid value-(F12; lbs./sel.--0.5 modified nucleic acid resin.

Lewisol 18 (Lewis): Color-N-WG; M. P. 0.; sold value 12-18; lbs/gel, es; reletively cheep resin. Compatible with Et cell. end chlorinoted rubber. (Modified meleic.)

Rezyl 99-4 (American Cyansmide): Complex chemical combinations of phthelic, etc, colds, elycerlne, etc. and modifying scents. This is 50% in toluol; op. g.-solid resin- L17; 50% solo. 1.01; lbs/gel. solid-9.8; stock solution-0.4; cove solution; color (I. P. 0: V. R.)--1L; ASTM softening point-55-56 0.; acid number-A4; eversge refractive index, 1.5205; 100% compatibility with NOa-cellulose, 10% compstioility to ethyl cellulose.

According to the present invention elhyd resins are incorporated with a, polymeric vinylidene chloride product to produce a mess which con be molded or extruded to form articles hevins e articles prepared from such compositions retain a high tensile strength. In many instances adsolids; soluble in M. T.; on. a 0.95; lbs. per gal, 0? dition of the alkyd resin has a, plosticinlnc eiiect.

particularly at elevated temperatures, and produces a mess that can easily be molded or extruded to form useful articles having a tough, durable, glossy finish and which retain a resist ance to chemicals typical of polymeric vinylidene chloride products. Furthermore addition of an alkyd resin to a polymeric vinyliclene ehloparticular alkyd resin to be employed may be mixed or ground together in a ball mill or other suitable mixer commonly employed in the plastic art, or they may be added to the polymer on hot rolls in a method similar to compounding rubb-er compositions. Another satisfactory method of incorporating the ellryd resin with the polymeric vinylidene chloride product is to dissolve the resin in a readilyvoletile solvent and mix or grind the materials in any suitable apparatus such as 9. ball mill, thereafter evaporating the solvent. To effect complete homogenization of the composition, it should preferably be heated to fusion temperature.

The following examples illustrate the practice of the invention but are not to be construed as limiting:

Example 1 A quantity containing 2.5 grams of Esterol 830, a solution of an oxidizing type of alkyd resin identified in Chemical and Metallurgical Engineering, vol. 41 (1934) at page 591, as being a glycerol-phthalic anhydride resin, and 5.0 grams of 1,2-epoxy-3-(Z-phenylphenoxy) propane, to serve as a. heatstabiiizer, were incorporated with 18 milliliters of acetone. To this solution was added 42.5 grams of a co-polymer consisting of 90 per chloride. The mixture was ground until thoroughly blended, and then dried. The composition could easily be molded or extruded and filaments,

having a diameter of 0.015 inch, prepared from easily be molded or extruded and filaments, having a diameter of 0.015 inch, prepared from this material were tough, shiny, flexible threads and had a tensile strength above 02,000 pounds per square inch. Rezyl resins are listed as glycerolphthalic anhydride resins in Chemical and Metallurgical Engineering, vol. 41 (1934) at page 595.

Ezampled A composition was prepared as in Example 1 g butsubstltuting Aroplaz 930, a solution of e nonpolymeric vinylidene chloride oxidizing type of e thermosettlng, pure clkyl resin, for the Esterol 830. The composition could eesiy be molded or extruded and filaments, hsving a diameter of 0.014 inch, prepared from this meterlal were flexible, shiny threads and had as tensile strength above 40,000 pounds per square inch.

Example 5 A composition was prepared as in Example 1 but substituting Rezyl 99-4, 9. solution of a nonoxidizing type or 2. fatty acid-modified alkyd resin, for the Esterol 830. The composition could easily be molded'or extruded and filaments, having a diameter of 0.016 inch, prepared from this 'material were translucent, flexible threads, with a waxy handle and had a tensile strength above 43,000 pounds per square inch. Rezyl resins are listed as glycerol-phthslic snhydride resins in Chemical and Metallurgical Enigneering, vol. 41(1934) at page 595.

Example 6 v 2.5 grams of Teglsc Z152, a natural resin-modifled, alkyd resin having e melting point of 120- 130 0., and 5.0 grams of 1 ,2-epoiw-3-(2-phenylcent vinylidene chloride and 10 per cent vinyl I this material were flexible, shiny threads and had a tensile strength above 43,000 pounds per square inch.

Example 2 A composition was prepared as in Example 1 but substituting Duraplex C-45, a solution of an 1 oxidizing type of an oil-modified, thermosetting alkyd resin, for the Esterol 830. The composition could easily be molded or extruded and filaments, having a. diameter of 0.014 inch, prepared from this material were translucent, flexible threads with a waxy'handle and had a tensile strength above 38,000 pounds per square inch.

The Duraplex resins are made by The Resinous- Products and Chemical Company, whose Synthetlc Resins catalog, April, 1941, at p e 18, de-

fines Duraplex resins as "oil-modified alkyds derived from phthalic anhydride, glycerine, and oil fatty acids."

. Example 3 A composition was prepared as in Example 1 but substituting Rezyl 1103, a liquid, oxidizing type of an unsaturated fatty acid-modified alkyd resin, for the Esterol 830. The composition could phenoxy) propane, to serve as a heat stabilizer, were incorporated with 20 milliliters of acetone. To this solution was added 42.5 grams of e. copolymer consisting of per cent vinylidine chloride and 10 per cent vinyl chloride. The mixture was ground until thoroughly blended and then dried: The composition could easily be molded or extruded and filaments having a diameter of 0.015 inch, prepared from this material were tough, shiny, threadsand had a tensile strength .above 44,000 pounds per square inch.

Example 7 A composition was'prepared as in Example 6 but substituting Amberlac D-96 an oil-modified thermomtting alkyd resin having a melting point of 104-106 C., for the Teglac Z-152. The composition could easlly be molded or extruded and filaments, having a diameteroi 0.013 inch, prepared from this material were flexible, waxy, translucent threads and had a tensile strength above 52,000 pounds per square inch.

Example 8 A composition was prepared as in Example 6 but substituting Paranol LB-89, a nucleic acidmodifi ed alkyd resin having a melting point of 82-09 C., for the Teplac 2-152. The composition could easily be molded or extruded and file.- ments, having a diameter of 0.015 inch, prepared from this material were shiny, flexible threads with a high gloss and had a tensile strength above 44,000 pounds per square inch.

Example 9 A composition was preparedas in Example 6 but substituting Paranol 1640, s. phenol-iormaldehyde resin-modified alkyd resin having a. meltin; point 01 116-130 $2., for theTeslac Z452.

essence The composition could easily be molded or extruded and filaments having s diameter of 0.015 inch, prepared from this material were shiny, tough threads and had a. tensile strength above 48,000 pounds per square inch.

Ecomple 1 o Eaccmple iii A quantity corresponding to 4.5 grams of solids of Aroplpz 936, a. solution of a. non-oxidizing type of s. thermosetting, pure clhyd'resin, and 0.5 gram of a co-polymer consisting of Q per cent vinylidine chloride and per cent vinyl chloride were placed in a. test tube and heated at about 165- C., until the materials were fused. The product was it tan colored, homogeneous, greasy paste.

Example 12 g A quantity. corresponding to 3.0 grams of solids of Esterol 830, a solution of a non-oxidizing type of a pure alwd resin, and 2.0 grams of a copolymer as in Example 9. were heated in a. test tube at about 165 0., until the materials were fused. The product was a. hard, brittle, homogeneous mass and had a brown color.

Example 13 3.0 grams of Iiewisol 18, a maleic acidmodified type of an alkyd resin having a meltingpoint of 95-98 (3., and 2.0 grams of a co-polymer as in Example 9 were heated to a fusion temperature.

The product was a light amber colored, homogeneous. brittle mass.

The compositions which contain relatively low proportions of the alkyd resin have improved molding and extruding properties, while the compositions which contain relatively large proportions of the alkyd resins will, depending on the type of alkyd resin used range from soft pastes to hard brittle masses. The latter compositions may be advantageously used in preparing improved lacquers, varnishes or points.

The proportion of alkyd resin to be employed in the new compositions depends upon the hardness, toughness, strength and flexibility desired in the modified composition. For example, compositions for use in injection molding must flow well at molding temperatures but should harden rapidly at lower temperatures. They should be hard enough when cold to withstand scratching and tough enough to withstand shock. Compositlono for use in making thin films, foils, or .i'llameats should have high flexibility at all temperaturcs met with in service, and be sumcicntly hard mo tough enough to withstand abrasion.

they are incorporated. when it is desired simply to produce a product having improved molding and extruding properties and which can be worked to form useful articles, threads, bands, filaments, foils and the like which retain the high tensile strength shown by the parent polymeric vinylidenechloride product the amount of alkyd resin willordinarily vary from about 0.5 to about per cent and more specifically from about 2 to about 7.5 per cent. When, however, it is desired to produce a polymeric vinyliclene chloride product which is substantially more compatible with many of the commonly used lacquer solventsthe amount of alkyd resin employed may very from about 10 to about 90 per cent.

While the above examples show the preparation of compositions from a. polymeric vinylidene chlo- .ride product consisting of o. co-polymer oi 90 per cent vinylidene chloride and to per cent vinyl chloride, incorporated with alkyd resins, other polymeric vinylidene chloride products which have wide commercial value and which may be advantageously used in preparing the new compositions, include the co-polymers containin from about 5 to about 30 per centof vinyl chloride and correspondingly from about 95 to about 70 per cent of vinylldene chloride. Other copolymers, in like proportions with vinylidene chloride. as included herein under the definition of the term, "polymeric vlnylidene chloride product," form equally valuable compositions.

In preparing molded or extruded articles from the newpolymeric vlnylidene chloride compositions at temperatures above their respective softening points, where the material is often maintained for a considerable period of time, it is desirable to have present in the composition a heat-stabilizing agent which acts to decrease or prevent thermal decomposition. Asubstance 40 which will also prevent darkening on exposure to light is often desirable. Compounds applicable for these purposes include 1,2-epoxy-3-(2-phenylphenoxy) propane, allyl-disulfide, z-chloroallyldisulflde, 2,2'-dihydroxy-bensophenone, tributyl aconitate, dipropyl maleate, 2-phenoxyethyl cinnamate, and di-(alpha-phenylethyl) other.

The incorporation of minor amounts of coloring agents, fillers, plasticizers and the like has also been found to be useful and desirable when used in such amounts that the desirable mechanical properties of the product are not affected.

Other modes of applying the principle of our invention may be employed instead of those explained, change being made as regards the materials" employedkprovided the product recited in the following claims be obtained.

' We therefore point out and distinctly claim as our invention.

1. A thermoplastic molding and extrusion composition, the essential ingredients or which are a vinylene chloride polymer in which vinylidene chloride constitutes at least 70 per cent of the polymer, and from about 2 to about 1.5 per cent of an alkyd resin based on the weight of the polymer.

2. A thermoplastic molding ond extrusion composition, the essential ingredients of which are a copolymer of from about 5 to about 30 per cent of vinyl chloride and correspondingly from about to about 70 per cent of vinylidcnc chloride. and from aboutzto about 7.5 percent of an alkyd resin based on thcweight o! the oopolymer.

EDGAR C. BRITI'ON. HAROLD W. IOLL. 

